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951

The Canadian Mineralogist


Vol. 43, pp. 951-963 (2005)

CRYSTALLOGRAPHIC CONTROLS ON TRACE-ELEMENT


INCORPORATION IN AURIFEROUS PYRITE FROM THE PASCUA EPITHERMAL
HIGH-SULFIDATION DEPOSIT, CHILE–ARGENTINA

ANNICK CHOUINARD§, JEANNE PAQUETTE AND ANTHONY E. WILLIAMS-JONES


Department of Earth and Planetary Sciences, McGill University, 3450 University Street, Montreal, Quebec H3A 2A7, Canada

ABSTRACT

The distribution of gold and other trace elements in the ore-stage pyrite from the high-sulfidation Au–Ag–Cu Pascua deposit
in the El Indio belt in north-central Chile was studied using electron-microprobe and secondary-ion mass spectrometry (SIMS)
imaging and analysis. The images show that concentrations of Au and Cu are concentrically zoned, and those of Ag, As, Se and
Te are zoned both concentrically and sectorally. The principal trace-element associations are As–Ag, Au–Cu and Se–Te. We
propose that the first two associations, As–Ag and Au–Cu, reflect coupled substitutions for Fe, whereas Te and Se replace S by
direct-ion exchange. The near-identical patterns of sector zoning of Ag and As suggest that silver enters the structure of pyrite via
a coupled substitution with As, in which one atom of Ag and one of As substitute for two Fe atoms, yielding (Ag+0.5As3+0.5)S2.
Gold and copper were excluded during an interval in which growth conditions promoted the development of | hk0 | sectors at the
expense of | 111 | sectors; their enrichment patterns show only slight evidence of sectoral preferences. With the analytical methods
employed, we could not distinguish unequivocally between incorporation of gold as minute inclusions of the native metal or a
coupled substitution of gold as an Au3+ ion and copper as a Cu+ ion for two Fe2+ ions, yielding (Au3+0.5Cu+0.5)S2. However, we
favor the latter interpretation. Incorporation of gold as Au3+ is also consistent with evidence of unusually oxidizing conditions
during the formation of the Pascua deposit. The zonation of invisible gold and associated trace elements in the ore-stage pyrite
at Pascua is the first documented example of crystallographic structural control of the surface on the incorporation of multiple
trace elements in pyrite. Moreover, the nature of this zonation provides clear evidence that incorporation of gold in pyrite does
not necessarily involve coupled substitution with arsenic, as proposed for many other deposits. Not only can arsenic behave as
a metal in the structure of pyrite, but its sectoral pattern of incorporation is a potentially sensitive indicator of redox conditions
during mineralization.

Keywords: gold, copper, silver, arsenic, selenium, tellurium, pyrite, sector zoning, high sulfidation, element-distribution maps,
electron-microprobe analysis, secondary-ion mass spectrometry, Pascua, Chile.

SOMMAIRE

La distribution de lʼor et autres éléments traces dans la pyrite de la minéralisation principale du gisement épithermal à
Au–Ag–Cu de Pascua, dans la ceinture de El Indio au centre-nord du Chili, a été étudiée par microsonde électronique et par
spectrométrie de masse des ions secondaires. Les concentrations de Au et de Cu sont zonées concentriquement, alors que celles
de Ag, As, Se et Te sont zonées concentriquement mais aussi en secteurs. Les associations principales des éléments-traces sont
As–Ag, Au–Cu et Se–Te. Nous croyons que les deux premières, As–Ag et Au–Cu, sont le produit de substitutions couplées au
site Fe, tandis que le Te et Se remplacent le S par échange direct dʼanions. La zonation en secteurs presquʼ identique de lʼargent
et de lʼarsenic fait penser que lʼargent est entré dans la structure de la pyrite via une substitution couplée avec lʼarsenic, selon
laquelle Ag et As remplacent deux atomes de Fe, donnant (Ag+0.5As3+0.5)S2. Lʼor et le cuivre ont été exclus durant un intervalle
correspondant à des conditions de croissances favorisant le développement des secteurs | hk0 | aux dépens des secteurs | 111 |. Ces
deux éléments ne montrent quʼune très faible préférence pour certains secteurs. La méthode dʼanalyse utilisée ne nous permet pas
de distinguer de façon non équivoque entre une incorporation de lʼor sous forme de minuscules inclusions du métal ou celle de
substitution couplée de lʼor sous forme de Au3+ et du cuivre sous forme de Cu+ pour deux ions de Fe2+, donnant (Au3+0.5Cu+0.5)S2.
Cependant, nous préférons cette dernière interprétation. Lʼinterprétation que lʼor est présent sous sa forme Au3+ plutôt que Au+
concorde avec les indices de conditions très oxydantes durant la formation du gisement de Pascua. La zonation des éléments traces
dans la pyrite de Pascua est le premier exemple documenté de contrôle crystallographique structural de la surface cristalline sur
lʼincorporation de multiples éléments traces dans la pyrite aurifère. De plus, la nature de la zonation met en évidence le fait que

§ E-mail address: annick@geol.queensu.ca


952 THE CANADIAN MINERALOGIST

lʼor nʼest pas nécessairement couplé avec lʼarsenic, tel que plusieurs ont proposé à dʼautres gisements de pyrite aurifère. Non
seulement lʼarsenic peut-il se comporter comme un métal dans la structure de la pyrite, mais sa zonation en secteurs pourrait
potentiellement servir dʼindicateur de conditions dʼoxydo-réduction durant la minéralisation.

Mots-clés: or, cuivre, argent, arsenic, sélénium, tellurium, pyrite, zonation sectorielle, fort degré de sulfuration, carte de distribu-
tion des éléments, microsonde électronique, spectrométrie de masse des ions secondaires, Pascua, Chili.

INTRODUCTION addition to economic considerations, the study of pyrite


serves to improve our understanding of an important
Gold is associated with trace elements such as host for environmentally significant elements such as As
Ag, As, Cu, Se and Te in the ore-stage pyrite of and Se (e.g., Hochella et al. 1999, Jambor et al. 2000,
the high-sulfidation epithermal Pascua Au–Ag–Cu Savage et al. 2000, Bostick & Fendorf 2003).
deposit, in northeastern Chile near the border with
Argentina. The “invisible” gold in this pyrite accounts GEOLOGY OF THE DEPOSIT
for approximately 50% of the ore reserves of the
deposit (274 Mt of Au; Chouinard et al., submitted). The Pascua high-sulfidation Au–Ag–Cu deposit,
Evidence from scanning electron microscopy (SEM), in northeastern Chile, and partially in Argentina,
electron-microprobe analysis and secondary-ion mass contains an estimated 225 million tonnes of ore with
spectrometry (SIMS), presented here, suggests that the an average grade of 1.98 g/t Au and 66 g/t Ag (Barrick
above elements are in solid solution within the pyrite, Gold Corporation, Annual Report, 2003). The Au–Ag
that their distribution is concentrically and sectorally mineralization occurred during the Miocene, and was
zoned, and that their incorporation was controlled crys- hosted mainly by Triassic granitic rocks and by Miocene
tallographically by the nature of the growth surfaces. breccia bodies composed mainly of altered Triassic
In contrast to most deposits studied thus far, gold at granitic rocks. Approximately 25% of the potentially
Pascua commonly displays an antithetic relationship economic reserves are hosted by Brecha Central, which
with As, and it appears to have been incorporated via a is the most important hydrothermal breccia pipe on the
coupled substitution with Cu. We seek here to explain property; it formed prior to mineralization.
the mechanism of incorporation of gold in pyrite from The host rocks underwent two stages of high-sulfida-
the Pascua deposit. tion alteration, the latter of which was accompanied
by main-stage Au–Ag–Cu mineralization. Early
BACKGROUND INFORMATION hydrothermal activity involved acidic condensates of
magmatic vapors (with pH values probably as low as
There is evidence that the incorporation of gold zero; Chouinard et al. 2005), and likely originated from
in pyrite is commonly associated with a substitution a porphyry intrusion at depth on the Argentinian side of
involving arsenic. The most widely held view is that the deposit; these fluids produced extensive and perva-
substitution of As for S at the growth surface promotes sive advanced argillic alteration, local development of
substitution of Au (as Au+) for Fe (e.g., Cabri et al. vuggy silica, and distal argillic to propylitic alteration.
2000, and references therein). However, Bostick & This alteration was locally followed by an intermediate,
Fendorf (1999) challenged this view, and showed that less acidic stage (possibly owing to an influx of mete-
As sorbed on pyrite is coordinated to sulfur atoms. oric water), which led to silicification and argillic and
Arehart et al. (1993) suggested that Au in arsenoan jarositic alteration, which was penecontemporaneous
pyrite was probably incorporated as Au3+ at the Fe site with the formation of Brecha Central. A renewal of
through coupled substitution with As1– at the S site. highly acidic hydrothermal activity produced a second
Finally, Simon et al. (1999a) suggested, on the basis stage of intense advanced argillic alteration and vuggy
of XANES spectra and TEM imaging, that arsenoan silica, and subsequent Au–Ag–Cu mineralization.
pyrite may represent mixing of pyrite with fine layers of The main stage of Au–Ag–Cu mineralization
arsenopyrite or marcasite-type phases, and that the gold coincided with the termination of the second stage of
is structurally bound in the latter as Au+ and Au0. alteration and involved precipitation of Au, either as the
Another important consideration is that models of native metal or as a solid solution in the structure of
trace-element incorporation in pyrite have been based pyrite and enargite. These metals are interpreted to have
on studies of samples from mineral deposits (sedi- been transported by the magmatic vapors responsible
ment-hosted, mesothermal and volcanic-rock-hosted for advanced argillic and vuggy silica and to have been
massive sulfide deposits) formed at near-neutral pH deposited as a result of their cooling and subsequent
and relatively reducing f(O2) conditions. There has been condensation (Chouinard et al. 2005).
very little attention paid to the trace-element content of Main-stage pyrite occurs in all sulfide-rich parts
pyrite deposited under the highly acidic and oxidizing of the deposit, and is distinguished from other types of
conditions required to form high-sulfidation deposits. In pyrite by crystals containing anomalous and distinctly
AURIFEROUS PYRITE, PASCUA EPITHERMAL DEPOSIT, CHILE–ARGENTINA 953

zoned concentrations of Au, Ag, Cu, As, Te and Se. acquired from a multichannel plate with fluorescent
This pyrite is generally finer grained than other types screen using a Photometrics Series 200 CCD camera,
of pyrite in the deposit, and locally may exhibit collo- and are 62.5 m in diameter. During collection of each
form banding, particularly at higher elevations. Its dull direct-ion SIMS image, the sample surface is sputtered
greenish luster and differential weathering arising from by a primary ion beam. As such, because of repeated
compositional heterogeneities facilitate its identification analyses, images may not be perfect replicas owing to
in the field. slight degradation of the mineralʼs surface.
Gold mineralization was followed by a sulfate
stage of alteration, represented by barite and anglesite RESULTS
at lower elevations, and these minerals plus primary
szomolnokite (FeSO4•H2O) at higher elevations. The In the sample containing grains of subhedral pyrite,
main stage of mineralization was followed by a stage concentration of Au and Cu are restricted to two main
of silver enrichment in the upper parts of the deposit, concentric zones, whereas Ag, As, Se and Te are
represented by sulfide-poor, halogen-bearing Ag zonally distributed both concentrically and sectorally.
minerals such as iodargyrite and chlorargyrite. This The mean concentrations of As and Cu, determined by
stage produced a blanket containing these minerals EPMA, are 0.08 and 0.24 wt%, respectively. The mean
above an elevation of ~4700 m, and represents the concentration of silver is 0.05 wt%, and it ranges from
final phase of hydrothermal activity (Chouinard et the detection limit (0.01 wt%) to 0.41 wt%. The concen-
al., submitted). Supergene alteration is manifested by tration of Se is generally below the detection limit (0.01
secondary jarosite and soluble sulfates (e.g., coquim- wt%). Quantitative SIMS analyses of ore-stage pyrite
bite, voltaite and chalcanthite), which formed as a result yielded an average of 45.2 ppm Au for 20 analyses and
of sulfide oxidation (Chouinard 2003). a range from 0.2 to 386 ppm (Chouinard 2003). The
The present study is based on the two best pyrite sample of colloform pyrite contains more As and Ag;
crystals available, which are typical of the gold-bearing the mean values are 0.25 and 0.08 wt%, respectively.
pyrite that formed during the main stage of Au–Ag–Cu Gold concentrations are consistently high in colloform
mineralization. Both crystals are from rocks containing pyrite, averaging 84 ppm and ranging from 69 to 121
mainly quartz–pyrite–enargite and szomolnokite; one ppm (Chouinard 2003).
of them is subhedral and from level 4680 m, and the Figure 1 shows element-distribution maps in the
other is a colloform variant collected at an elevation of subhedral crystal of pyrite (Table 1). During Stage
approximately 4800 m. II, the growth sectors were strikingly defined by their
differential enrichment in As and Ag (Fig. 1) and, to a
ANALYTICAL METHODS lesser extent, Se and Te. With the exception of the inner
of the two main concentric zones, in which all elements
Element-distribution maps and spot analyses were were incorporated, zones with elevated Cu generally
made using wavelength-dispersion spectrometry correspond to zones low in As and Ag, and vice versa;
(WDS) and a JEOL JXA–8900L instrument at McGill Se and, to a lesser extent, Te also are concentrated in the
University. Quantitative electron-probe micro-analyses outer concentric zone. The four main stages, numbered
(EPMA) were conducted at 20 kV, and a beam current from I to IV in Figure 1C, suggest at first glance an
of 40 nA. The following standards and analytical lines alternation of growth habits between cubic (Stage I
were employed: pyrite (FeK, SK), FeAsS (AsL), and III) and octahedral (Stage II) sectors. We could
AuTe2 (AuM, TeL), AgBiSe2 (AgL, SeL), ZnS not resolve the zoning pattern of Stage I. However, the
(ZnL) and CuFeS2 (CuK). Peak and background were striking pattern of sectoral enrichment seen in Stage II
counted as follows: Fe (20 s), S (20 s), As (100 s), Au
(200 s), Te (150 s), Ag (150 s), Se (150 s), Zn (100 s)
and Cu (50 s). For elements not detected, means were
calculated using half the detection limit.
Direct-ion images and quantitative secondary-ion
mass spectrometry (SIMS) analyses were made at
CANMET/MTL in Ottawa using procedures described
in Cabri & McMahon (1995) and McMahon & Cabri
(1998). Analyses were conducted using a Cameca IMS
4f instrument and a Cs+ primary ion beam on carbon-
coated polished thin sections of the two crystals. For
quantitative analyses, the gold content was established
with relative sensitivity factors (RSF) established from
depth profiles on standards with known contents of gold.
The minimum detection-limit for Au in pyrite is 0.04
g/t (40 ppb). Direct-ion images for all elements were
954 THE CANADIAN MINERALOGIST

FIG. 1. X- ray (EMP) maps of A) Cu, B) Fe, C) Ag, and D) As in ore-stage pyrite from the Brecha Central area (4680 m eleva-
tion). The numbers in C indicate the various growth-zones described in the text, whereas numbers in D indicate locations of
quantitative EMP spot-analyses, the results being presented in Table 1. The distribution of sulfur is not shown, but is very
homogeneous. The bright spots on the Cu and As images are soluble sulfates, whereas the bright areas on the Ag image are
due to late iodargyrite and chlorargyrite. The map dimensions are 275  275 m. Direct-ion SIMS images of the core of
this pyrite grain are presented in Figure 3.

of the subhedral pyrite at Pascua is best explained by a reasonable approximation. Stage III coincides with a
a combination of {111}, {110} and {hhl} forms that waning of the | 110 | sectors and the appearance of the
was modeled with the SHAPE software (Dowty 1999; steeper {hhl} faces. The growth-sector boundaries do
Fig. 2). The | hhl | sectors could not be indexed precisely, not merge toward the center of the crystal, indicating
but models of the wide concentric zones throughout that the section is slightly off-centered.
Stage II suggest that {hhl} faces are only slightly SIMS images of a section through the core of the
inclined relative to those of a (100) cube, and {113} is crystal (Fig. 3) show relative enrichment patterns for
AURIFEROUS PYRITE, PASCUA EPITHERMAL DEPOSIT, CHILE–ARGENTINA 955

FIG. 2. Reconstruction of the zoning geometry using SHAPE (Dowty 1999). A. Sectoral zoning during Stage II is best explained
by a growth morphology dominated by the {111} octahedron having a low affinity for most trace elements. Trace elements
were preferentially enriched in the sectors of a {110} dodecahedron. A third form, tentatively indexed as {113}, explains the
pinching out of the | 110 | sectors prior to the impurity-rich concentric zone at the beginning of Stage III. B. Cross-section
(slightly off-center) through the crystal shown in A. C. The discontinuous zoning (white arrows) in the outer, impurity-rich
concentric zone (Stage III) of the SIMS map for As suggests that selective incorporation was sensitive to the orientation of
the growth steps. D. Faces of the {111} octahedron are normally covered with three-sided growth hillocks on which growth
steps oblique to the isometric axes are related by symmetry. E. Prior to the beginning of Cu and Au incorporation, the change
in the pattern of zoning suggests the waning of | 110 | sectors. A more complex pattern of zoning developed within the | 111 |
sectors, suggesting the presence of non-equivalent vicinal faces. F. The zoning pattern is consistent with the presence of
more complex growth-hillocks, where new steps on opposite sides are unrelated by symmetry and could therefore display
different affinities for trace elements.
956 THE CANADIAN MINERALOGIST

A B

C D

E F

FIG. 3. Direct-ion SIMS images of A) Au, B) As–Cu–Au, C) Cu–Au, D) As–Au,


E) Se–Au, and F) Te–Au of the core of the zoned crystal of pyrite shown in Figure 1.
The dark area near the center of all images is a hole. The images show a positive cor-
relation between concentrically zoned Au and Cu and, to a lesser extent, between Au
and As, as well as between sectorally zoned Ag (from Fig. 1) and As. Note the clear
affinity of Ag, As, Se and Te for the {111} octahedral sectors. The temporal trends of
Te and Se from core to rim, within {111} sectors, are nearly exactly the opposite of
those of As and Ag, which reach maximum incorporation near the center of the crystal.
A combination of green and red will produce yellow, whereas blue and red will produce
pink. The field of view is 62.5 m and is entirely in pyrite.
AURIFEROUS PYRITE, PASCUA EPITHERMAL DEPOSIT, CHILE–ARGENTINA 957

Cu and As similar to those mapped with the electron composition), whereas sectoral zoning indicates a
microprobe. In addition, the SIMS images resolve the stereochemical influence of the crystal-surface structure
distribution patterns for Au, Te and Se, the concentra- on the incorporation of trace elements.
tions of which are too low either to be detected or to
provide interpretable patterns by electron-microprobe Constraints on pyrite morphology
mapping. The distribution of Au and Cu defines sharp and crystal-surface structure
concentric zones (Stage I, and at the transition from
Stage II to III). Within these zones, Au and Cu do not Only three forms make up the majority of pyrite
show the obvious sectoral preferences observed for crystals: the cube {100}, the octahedron {111} and the
other trace elements, such as Ag, As, Se and Te. Details pyritohedron {210}. However, many more have been
of the Stages I and II of growth visible in electron- documented. Sunagawa (1957), in particular, noted the
microprobe maps of Figure 1 are shown in the SIMS prevalence of {hk0} forms in many Japanese hydro-
elemental maps of Figure 3. The exclusion of Au and Cu thermal replacement deposits.
during Stage II is particularly noticeable. In contrast, Ag Poisoning and enhancement of the {111} face by
(Fig. 1C), As, Te and Se were incorporated throughout As were documented in several Japanese deposits by
all stages, but they show specific sectoral preferences Sunagawa & Takahashi (1955) and Hayashida & Muta
during Stage II, at which point all four elements were (1952). Yet, despite interesting trends in pyrite habits
preferentially incorporated on | 110 | rather than | 111 | within ore deposits, there has been very little experi-
sectors. However, more subtle similarities are also mental work on the controls of pyrite morphology.
noticeable for specific pairs of elements: within | 110 | One notable contribution was that of Murowchick &
sectors, Ag (Fig. 1C) and As concentrations are highest Barnes (1987), who documented the effect of tempera-
at the beginning of Stage II, where the | 111 | sectors ture and degree of supersaturation on hydrothermally
first expanded, whereas Te and Se concentrations were grown pyrite between 250 and 500°C. They noted that
highest toward the end of Stage II. The preference increasing supersaturation induced by cooling promoted
of selenium for the | 111 | sectors over | 110 | sectors transitions in habit from the cube to octahedron, and
is weaker than the differential sectoral incorporation speculated that other processes, including mixing with
displayed by Ag, As or Te. A slight deviation of the oxidizing groundwater, might induce similar changes in
section from the (001) plane by 2–3° easily accounts for habit, if supersaturation increases as a result of oxida-
the fact that the highest concentrations of Se and Te are tion of the sulfide species to form S22– or HS2–.
restricted to a single opposing pair of | 110 | sectors.
The colloform pyrite does not show obvious crystal- Controls on the distribution of Se, Te, Ag and As
lographic faces, but SIMS images distinguish concentric
bands, which provide evidence of temporal fluctuations Stage II is characterized by strong differential
of Cu, Au, As and Se incorporation (Fig. 4). No data are partitioning of Ag, As an Te, which were preferentially
available for Ag and Te in this sample. A decrease in incorporated on the {110} faces and rejected by the
sulfur concentration in concentric zones generally corre- {111} faces. Sectoral zoning is less pronounced for
sponds to an increase in Se concentration. However, selenium, which was incorporated on both types of
trace-element concentrations are too low to account sectors. Copper and gold were apparently excluded
for the significant depletion in S, which could be due from the pyrite surfaces during this stage.
to the uneven surface of pyrite, or to the presence of Two types of control are generally invoked to
minor Fe-bearing soluble sulfates, which are common explain sectoral zoning. In the first type, differential
at Pascua. As in the subhedral Au-bearing pyrite, the growth-rates among non-equivalent forms have been
distributions of Au and Cu, and to a lesser extent Se, are documented as a controlling factor in the partitioning of
positively correlated (this statement refers only to zones trace elements (Burton et al. 1953, Hall 1953, Watson
interpreted to consist, exclusively or dominantly, of & Liang 1995). In the second type, well documented in
pyrite, on the basis of the high concentration of sulfur). minerals of the apatite group (Rakovan & Reeder 1994),
Similarly, the enrichment patterns of As are mainly anti- in calcite (Paquette & Reeder 1995), in topaz (Northrup
thetic to those of Au and Cu, and overlap only slightly & Reeder 1994) and in fluorite (Bosze & Rakovan
with the Au- and Cu-bearing concentric bands. 2002), the role of surface structure on the differential
incorporation of trace elements in a growing crystal has
DISCUSSION emerged as a major mechanistic control.
Pyrite has a halite-like structure, with iron ions
The presence of concentric and sector zoning in the arranged in a face-centered cubic lattice and alternating
subhedral pyrite suggests two different types of control with a face-centered lattice of S2 dimers. In other,
on trace-element incorporation in pyrite. Concentric simpler ionic cubic structures, such as halite, the higher
zoning records temporal changes and variations in tolerance of {111} for impurity incorporation relative
conditions of pyrite precipitation (temperature or fluid to {100} faces is well documented, and the presence
958 THE CANADIAN MINERALOGIST

of additives during crystal growth tends to promote the with recent studies, including that of Helz et al. (1995),
development of | 111 | sectors at the expense of | 100 | who suggested that thioarsenic species are important at
(Boistelle & Simon 1974). Investigations of the struc- low temperature and in sulfide-rich solutions, although
ture of the {100} and {111} pyrite surfaces by scanning the stoichiometry of the predominant species remains
tunneling microscopy confirm that these surfaces differ uncertain (Wood & Samson 1998). Bostick & Fendorf
little from what would be expected from the bulk struc- (1999, 2003) used data on X-ray absorption fine-struc-
ture (Rosso et al. 1999). In their studies of the oxidation ture spectroscopy (XAFS) and Raman spectroscopy
of the {100} and {111} surfaces of pyrite, Guèvremont obtained on pyrite surfaces to show that sorbed As is
et al. (1998) and Elsetinow et al. (2000) demonstrated coordinated to S, and concluded that anion sorption of
that the latter are significantly more reactive than the As to sulfide minerals may not be correctly modeled as
{100} faces. They suggested that alternating Fe-rich simple ligand-exchange reactions.
and S-rich outermost surfaces, which are a feature of The striking correlation of Ag and As, in their
the {111} faces, could be responsible for their higher sectoral preferences, and their temporal variation within
reactivity. If differences in surface structure influence the octahedral sectors of Stage II, suggest that both
reactivity, they could also be expected, to some degree, ions entered the structure of pyrite as part of a coupled
to result in differential incorporation of impurities substitution. A charge-balanced scenario would be: Ag+
among at least some nonequivalent growth-sectors of + As3+ ↔ 2Fe2+ yielding (Ag+0.5As3+0.5)S2. This substi-
pyrite. However, the sectoral pattern suggests that the tution likely creates a distortion of the pyrite cell with
main control on differential incorporation may have Ag+ + As3+ having combined ionic radii of 201 pm (129
been the specific orientation of growth steps, rather than and 72 pm, respectively; Shannon 1976) compared to
overall differences in face structure. Throughout Stage 150 pm (Shannon 1976) for the two iron ions replaced.
II, the {111} sectors that discriminated against Ag, As, Of the two impurities, the ionic radius of As3+ is the
Te and Se throughout Stage I and II are typically domi- closer to the radius of Fe2+. For this reason, we suggest
nated by steps oblique to the isometric crystallographic that the As would be more easily incorporated in the
axes. Incorporation was favored on {110} faces, where crystal structure. The charge imbalance would then
growth occurs on steps parallel to the isometric crystal- promote the coupled replacement of an adjacent Fe2+
lographic axes. ion by the larger silver ion.
Sectoral zoning, less pronounced in Stage III than Both Se and Te can readily replace S, but the radius
in Stage II, was characterized by increased overall of the selenide (232 pm) and telluride (250 pm) ions
trace-element enrichment. The abrupt reversal of these is substantially larger than that of the sulfide ion (219
patterns of relative enrichment from Stage II to Stage pm; Huheey et al. 1993). Selenium and Te substitution
III is consistent with a transition from | 110 | growth for S would locally increase the unit-cell dimensions,
sectors to | 113 | sectors. The abrupt shift of growth- possibly making the surface of pyrite locally more
sector boundaries across concentric zones of Stage III amenable to the incorporation of Au, Cu, As and Ag for
suggests that the character of {111} surfaces may have Fe. During Stage II, the temporal trend of Se incorpora-
also changed substantially. The | 111 | sector, usually tion is exactly opposite to those of As and Ag, and the
dominated by triangular growth-hillocks, may well have increase in Se at the transition between stages II and
broken down into two distinct sets of vicinal sectors, III correlates well with the increase in Cu, followed by
each dominated by steps that are parallel but unrelated Au incorporation. It is significant that Se, which shows
by symmetry, with different preferences of trace- the least evidence of temporal variation and only slight
element incorporation (Fig. 2d). In diamond, similar differential partitioning between | 111 | and | hk0 | sectors,
patterns of nitrogen zoning are produced by growth on also shows the least misfit with S as an anionic species.
non-equivalent sets of steps on the {100} and {111} Selenium is thus the most logical candidate of any of the
faces (Frank et al. 1990). trace elements for isomorphic substitution. Tellurium,
Natural As-rich pyrite can contain up to 8.4 wt% which forms a sensibly larger anion, was incorporated
As, but the chemical state of the arsenic is not known in smaller amounts and was more efficiently excluded
with certainty (Arehart et al. 1993, Fleet et al. 1993, by {111} than {hk0} during Stage II.
Mumin et al. 1994). Based on XANES spectra, Simon Because of their narrow band-gap, reactions at the
et al. (1999a) suggested that arsenic probably occurs in surface of semiconducting minerals are highly sensitive
the As– state, substituting for S and in a structural posi- to the electronic structure of surface sites. It is overly
tion similar to that in arsenopyrite. They also suggested simplistic to explain impurity incorporation in pyrite in
that arsenic is possibly concentrated in submicrometric terms of ionic radii, but the correlation of ionic size with
lamellae of marcasite or arsenopyrite within arsenoan relative trends of sectoral anionic substitution suggests
pyrite. In light of the strong crystallographic selectivity the importance of surface site-configuration. Becker et
on arsenic distribution and its coupled substitution al. (2001) recently emphasized the importance of step
with Ag in the Au-bearing pyrite at Pascua, we suggest reactivity in adsorption and redox-reaction kinetics of
that As is more likely to be incorporated as a cation semiconductors such as galena and pyrite. An important
substituting for Fe2+. This interpretation is in agreement factor in impurity incorporation within the Pascua pyrite
AURIFEROUS PYRITE, PASCUA EPITHERMAL DEPOSIT, CHILE–ARGENTINA 959

may well have been the persistence of the strongly divided into two substages. The first one is characterized
stepped {hh0} and {hhl} faces instead of the smoother by the incorporation of As along concentric zones, then
faces of a {100} cube or a {111} octahedron. The pres- by the incorporation of As and Au at the termination of
ence of steps with different redox-reaction kinetics, the As zone. The second substage is characterized by
coupled with the possibility of incorporating arsenic as the incorporation of both Au and Cu within a second
a cation or anion, could modify the electronic structure concentric zone enriched in Cu. The association of Au
of near-surface layers and profoundly influence the and As is nearly absent in the colloform pyrite, in which
adsorption and eventual incorporation of other metallic Au shows a strong positive correlation with Cu. Thus,
cations. although there is locally a positive correlation between
Evidence from phase-stability relationships indi- levels of Au and As, the strong positive correlation
cates that high-sulfidation deposits typically form between concentrations of As and Ag, and of Au and
in very oxidizing and acidic environments (Cooke Cu, are compelling evidence that, for the most part, Au
& Simmons 2000). Such an environment appears to and As were incorporated separately, i.e., they were not
have been the case at Pascua, where alteration and linked in a coupled substitution. We therefore focus the
mineralization assemblages are interpreted from phase remainder of this discussion on the Au–Cu association,
equilibria to have formed at a log f(O2) greater than rather than the well-known Au–As association, which
–32 and a pH of around 0 (at 250°C; Chouinard et al., has been explained satisfactorily by a coupled substitu-
submitted). Hochella et al. (1999) noted that oxida- tion in which As and Au replace S and Fe, respectively
tion of {100} pyrite surfaces observed by scanning (reviewed above).
tunneling microscopy is not random but proceeds in An important consideration in explaining the incor-
patches bounded dominantly by the <110> direction. poration of Au is its size relative to the Fe2+ ion, which
The complex morphology of pyrite at Pascua and it must replace, and another is its charge. The atomic
the preferential incorporation of elements such as Ag radius of Au+ and of Au3+ is 151 and 99 pm, respec-
and As on specific sectors may therefore have been tively, whereas that of Fe2+ is only 75. We propose
enhanced by step kinetics reflecting these unusually that ionic size and charge constraints are satisfactorily
oxidizing conditions. met only if Au enters the pyrite structure as Au3+ in a
coupled substitution with Cu+ (91 pm) according to the
Controls on the distribution of Au and Cu coupled reaction Au3+ (99 pm) + Cu+ (91 pm) ↔ 2Fe2+
(150 pm). Moreover, we note that the larger average size
In the Au-bearing pyrite presented in Figure 3, of the substituting cations is readily accounted for by
gold and copper are restricted to two concentric zones substitution of Se– (232 pm) for S– (219 pm), which as
(Stages I and III). Gold is distributed less evenly along noted earlier is the only ion to concentrate strongly with
these zones than copper. Neither gold nor copper Au and Cu ions in the outer of the two main concentric
displays the strong sectoral preference noted for Ag zones. This interpretation is consistent with the low
and As. These direct-ion SIMS images have a resolu- pH and high f(O2) associated with the formation of
tion of approximately one micrometer (G. McMahon, high-sulfidation deposits, which would have favored
pers. commun., 2003), and therefore, do not allow us formation of Au3+.
to clearly exclude the presence of scattered submicro- Although this hypothesis satisfactorily explains the
scopic inclusions of native Au or other Au-bearing incorporation of Au, it does not explain the fact that the
phases. Heasman et al. (2003) used EXAFS data to concentration of Cu in the pyrite is appreciably higher
calculate the size of Au clusters in pyrite and determined than that of Au. It is therefore possible that some copper
a probable minimum size between 27 and 36 Å. On entered the structure of pyrite independently of gold. In
the other hand, Yang et al. (1998) used TEM images to principle, it could have been incorporated as Cu2+ by
document individual spheres of Au with an average size direct substitution for Fe2+. However, available experi-
of 0.15 m on growth surfaces of pyrite. Their TEM mental data for both aqueous liquid and vapor suggest
images have a dark appearance and do not reveal the that copper in most ore-forming systems is transported
presence of gold clusters. Considering that gold and as Cu+ (Xiao et al. 1998, Archibald et al. 2002). Thus,
copper concentrations correlate very well, we suggest if copper was incorporated separately from gold, it
that most of the Au and Cu were incorporated directly is unlikely to have entered the structure by simple
into the structure of pyrite. substitution for Fe2+ but rather by a more complex
In contrast to most other documented occurrences of path involving oxidation of Cu+. If this were the case
invisible gold in pyrite, at Pascua, the distribution of Au for copper, it is also possible, as has been suggested by
in ore-stage pyrite commonly correlates far better with Maddox et al. (1998), that Au was incorporated into
Cu and Te than with As (e.g., Cabri et al. 1989, Cook & the structure by being adsorbed as a charged species
Chryssoulis 1990, Arehart et al. 1993, Fleet et al. 1993, (Au3+ or Au+) that was subsequently reduced to Au0.
Fleet & Mumin 1997, Tarnocai et al. 1997, Yang et al. This hypothesis does not, however, explain the strong
1998, Simon et al. 1999a, b, Ashley et al. 2000, Cabri correlation of Au with Cu and Se.
et al. 2000). Incorporation of Au during Stage III can be
960 THE CANADIAN MINERALOGIST

A B

C D

E F

FIG. 4. Direct-ion SIMS images of A) Au, B) As–Cu–Au, C) Cu–Au, D) As–Au,


E) Se–Au, and F) S in the colloform variant of the ore-stage pyrite. The dark ovoid
areas in the S map probably reflect inclusions leached from the pyrite. A decrease in S
corresponds to an increase in Se concentration in some of the growth bands, but also
likely corresponds to the presence of Fe-bearing soluble sulfates. Elemental correlations
are similar to those of the subhedral pyrite, i.e., Au is mostly coupled with Cu, rather
than As. A combination of green and red will produce yellow, whereas blue and red will
produce pink. The field of view is 62.5 m and is entirely pyrite.
AURIFEROUS PYRITE, PASCUA EPITHERMAL DEPOSIT, CHILE–ARGENTINA 961

We cannot resolve the exact morphology of the AEWJ by NSERC and Barrick Gold Corporation. Dr.
crystals during Stage I, which coincided with the earliest Greg McMahon and Gilles Laflamme at CANMET
incorporation of Cu and Au. However, Stage III in provided valuable assistance on the technical aspects
subhedral pyrite shows an abrupt decrease in sectoral of SIMS analysis and imaging. The manuscript was
discrimination toward all the trace elements studied as improved significantly by constructive reviews from
well as an abrupt decrease in importance of the {110} S. Chryssoulis and R.R. Seal II, and the suggestions
sectors. This change in habit may reflect a change in of R.F. Martin.
bulk composition of the fluid, which could also have
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